Mary E. Rochford, the first woman to serve as superintendent of schools in the Archdiocese of Philadelphia, will step down June 30.
Rochford, who has held the post for nearly four years, said she was resigning to provide physical care for members of her family who could not care for themselves.
The archdiocese said that it had accepted Rochford's resignation "with great reluctance."
Rochford has worked in the Office of Catholic Education since 1999 and became superintendent of schools in the five-county archdiocese in July 2008.
In the past year, she worked closely with a Blue Ribbon Commission that recommended closing several schools as part of broad restructuring plan of Catholic education in the diocese.
A former nun, Rochford was a Catholic school teacher and administrator for more than 25 years.
The archdiocese said the Office of Catholic Education has begun a search for her successor.